Alkoxylated fluoro esters carboxylates

ABSTRACT

The invention relates to a series of novel alkoxylated fluoro esters which contain a terminal carboxy group. This class of compounds provides unique solubility in many organic solvents as well as very substantive salts of the carboxylic acid when neutralized with base. In addition, the compounds of the present invention have tremendous spreadability when applied to substrate. The compounds of the present invention are prepared by reacting a the hydroxyl group in a fluoro alcohol with an anhydride.

RELATED APPLICATIONS

This application is a divisional application of Ser. No. 09/017,333filed Feb. 2, 1998, now U.S. Pat. No. 5,969,177.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a series of novel fluoro alkoxylatedesters which have a terminal carboxy group. These materials provideoutstanding lubrication, and softening when applied to a variety offiber substrates. The compounds of the present invention are prepared byreacting a fluoro alcohol and an anhydride.

2. Arts and Practices

U.S. Pat. No. 5,296,625 to O'Lenick et al, incorporated herein byreference, discloses silicone carboxylate esters. The compounds of theO'Lenick et al invention are softeners and conditioners, but as willbecome clear are not good spreading agents. The ability to provide thinfilms to plastic and other substrates was lacking in the O'Lenick et alproducts.

The compounds of the present invention address deposition on fabric andskin of a highly lubricious, cost-effective lubricant. In addition, thecompounds of the present invention have tremendous spreadability whenapplied to substrate. This spreadability results in thin, highlylubricating films. The thinness of the film makes the delivery of anexpensive fluoro compound cost-effective on many substrates, since theweight of film per area of substrate treated is quite surprisingly low.The compounds of the present invention find use not only in applicationson substrate like plastics and textile fibers and fabric, but can beused in personal care products, like shave cream and hair conditioners,where the lubrication afforded by using the compounds of the currentinvention provide a close, more comfortable shave and outstanding wetcomb properties on hair.

THE INVENTION OBJECT OF THE INVENTION

It is the object of the present invention to provide novel alkoxylatedfluoro ester having a carboxy group present. These compounds areoutstanding lubricants that are substantive to the surface of a fiberand other textile materials including cellulosic material and haveincreased solubility in fatty materials including mineral oil, fattytriglycerides and traditional fatty quaternary ammonium compounds. Thecompounds of the present invention render the lubricity and bycontrolling the amount and placement of alkylene oxide in the molecule,can have significantly different solubilities in water. In oneembodiment, the compounds have a high cloud point due to the presence ofa polyoxyethylene group. This allows for deposition on fabric and skinupon heating. In addition, the compounds of the present invention havetremendous spreadability when applied to substrate. This spreadabilityresults in thin highly lubricating films. The thinness of the film makesthe delivery of an expensive fluoro compound cost effective on manysubstrates, since the weight of film per area of substrate treated isquite surprisingly low.

It is another objective of the current invention to provide fluoro estercarboxylates which can be used in personal care, textile, and industrialformulations to render softness and lubrication to the substrates beingtreated. The superior solubility properties are an important benefit,since this is a major aspect of consumer perception of softness inconsumer and industrial laundry applications. Application of thecompounds of the invention can be from solvent, aqueous dispersion orsolution, or applied neat in these processes.

SUMMARY OF THE INVENTION

The present invention relates to novel fluoro alkoxylated esters whichcontain carboxyl groups. The compounds by virtue of the polyoxyalkylenegroup are soluble in a variety of organic and aqueous systems, but havemany of the functional softening and lubrication properties of fluorocarbons. The solubility of these materials can be altered by simple pHadjustment. In the acid form these materials are fluoro-like it theirsolubility parameters. At higher pH values they become soluble inaqueous systems. This property makes these materials excellent additivesfor highly effective surface modifying finishes for fiber and textiles.The compounds of the present invention are substantive to cellulosic andsynthetic fibers as well as metal surfaces and plastic polymers.

As will become clear from the disclosure, the compounds of the presentinvention while having fluorine groups present in the molecule, haveunique solubility aqueous systems. This property is a direct result ofthe structure. The pendant group needs to contain (a) a fluoro grouplinked covalently through two methylene groups to (b) an alkoxylatedportion linked covalently to (c) an ester function, linked covalently to(d) an R" linking group containing carbon atoms linked covalently to (E)a COOH group. Compounds lacking these functional parts do not give thedesired solubilization properties. Optionally the carboxyl group can beneutralized with a base or an amine to give an ionic compound.

The compounds of the present invention therefore have a pendant groupwhich is as follows: ##STR1## wherein; EO is --(CH₂ CH₂ O)--

PO is --(CH₂ --CH(CH₃)CH₂ --O)--

The fluoro Group is soluble in fluoro carbon based materials; thealkoxylate group renders water solubility to the molecule; the esterlinkage taken with the carbon linkage group made up the oil solublegroup and the terminal group is the ionizable group.

These materials will allow for the solubilization of water, and fluorocarbons into one phase. Standard surface active agents or surfactantshave only water soluble portion and an oil soluble portion. A standardfatty surfactant has only a fatty and a water soluble: ##STR2##

This type of material will allow for solubilization of fatty oils andwater, but not fluoro carbons.

Fluoro carbons, on the other hand have a fluoro portion and a watersoluble portion. These materials allow for the solubilization of fluorocarbons, but not water.

There are many instances where there is a desire to make water andfluoro carbon stay in a single system. Each component is insoluble ineach other. The compounds of the present invention not only allow forpreparation of water in fluoro hydrocarbon emulsions, but alsofluorocarbon in water emulsions.

The compounds of the present invention are prepared by the reaction ofan anhydride with a fluoro alkoxy alcohol. Suitable anhydrides for thepreparation of the compounds of the present invention are cyclicanhydrides, which react easily at mild conditions with the hydroxylgroup to produce an ester carboxylate. Typical of the reaction is thefollowing sequence utilizing succinic anhydride: ##STR3##

The Fluoro--OH represents the hydroxyl group on the fluoro hydrocarbondescribed elsewhere in the disclosure.

The compounds of this invention are fluoro ester carboxylates made bythe reaction of an anhydride and a hydroxy containing fluoro compound.The compounds of the present invention conform to the followingstructure:

    CF.sub.3 (CF.sub.2).sub.x CH.sub.2 CH.sub.2 --O--R--C(O)--R"--C(O)--OH

wherein; ##STR4## R₁ is alkyl having from 1 to 20 carbon atoms; a, b andc are integers independently ranging from 0 to 20,

x is an integer ranging from 1 to 10.

PREFERRED EMBODIMENTS

In a preferred embodiment, a+b+c is greater than zero.

In another preferred embodiment, the R" is --CH₂ --CH₂ --.

In still another embodiment R" is --CH═CH--.

In another preferred embodiment R" is --CH₂ --C(R¹)--H.

In still another preferred embodiment R" is ##STR5##

In still another preferred embodiment R" is ##STR6##

In still another preferred embodiment R¹ is alkyl having from 6 to 20carbon atoms.

In a more preferred embodiment R¹ is alkyl having from 12 to 20 carbonatoms.

EXAMPLES

The compounds of the present invention are prepared by the reaction of ahydroxy fluoro compound and an anhydride. Examples of suitable reactantsare as follows:

REACTANTS Anhydrides

The various anhydrides listed are all items of commerce and are preparedby methods known to those skilled in the art.

Reactant Example I (Succinic Anhydride) ##STR7## Reactant Example II(Alkyl Succinic Anhydride) ##STR8## Reactant Example III (Alkyl SuccinicAnhydride) ##STR9## Reactant Example IV (Alkyl Succinic Anhydride)##STR10## Reactant Example V (Alkyl Succinic Anhydride) ##STR11##Reactant Example VI (Alkyl Succinic Anhydride) ##STR12## ReactantExample VII (Maleic Anhydride) ##STR13## Reactant Example VIII (PhthalicAnhydride) ##STR14## Reactant Example IX (Tetrachlorophthalic anhydride)##STR15## Hydroxy Fluoro Compounds

Many manufacturers offer a series of hydroxy fluoro compounds suitablefor use as raw materials in the preparation of the esters of the presentinvention. These materials are marketed under the many trade names.Dupont manufacturers and offers the compounds commercially.

A key structural attribute of the compounds of the present invention isthe two methylene groups between the fluoro part of the molecule and theoxygen. The structure of the stable alcohol is CF₃ (CF₂)_(x) CH₂ CH₂--OH. If the two methylene groups (--CH₂ --) are absent the alcohol isnot stable to hydrolysis.

    ______________________________________                                        Example      x     a           b   c                                          ______________________________________                                        1            1     20          20  20                                           2 2 10 5 10                                                                   3 4 0 10 0                                                                    4 6 5 5 5                                                                     5 8 0 0 0                                                                     6 10 5 1 5                                                                    7 8 10 0 0                                                                    8 10 5 0 0                                                                  ______________________________________                                    

General Reaction Conditions

The reaction can be run with either a stiochiometric amount of theanhydride, or an excess of fluoro polymer.

Into a suitable round bottom, three neck flask equipped with athermometer and a nitrogen sparge is added the specified number of gramsof the specified fluoro compound and the specified number of grams ofthe specified anhydride. The reaction mass is blanketed with nitrogen,and heated to 80 and 110 C. under the inert nitrogen blanket. Withinfour to five hours the theoretical acid value is obtained. The productis a clear liquid and is used without additional purification.

Example 9

Into a suitable round bottom, three neck flask equipped with athermometer and a nitrogen sparge is added 2468.0 grams of fluoroexample 2 and the 100.0 grams of succinic anhydride. The reaction massis then blanketed with nitrogen and heated to 80 and 110 C. Thistemperature is maintained for four to five hours. The theoretical acidvalue is obtained. The product is a clear liquid and is used withoutadditional purification.

Examples 10-17

Example 9 is repeated only this time substituting the specified numberof grams of the anhydride specified and the specified type and number ofgrams of fluoro compound as shown below;

    ______________________________________                                                Anhydride                                                                     Reactant          Fluoro Compound                                     Example   Example  Grams      Example                                                                              Grams                                    ______________________________________                                        9         I        100.0      1      3303.0                                     10 II 115.0 2 2468.0                                                          11 III 269.0 3 1103.0                                                         12 IV 185.0 4 1348.0                                                          13 V 316.0 5 713.0                                                            14 VI 340.0 6 1253.0                                                          15 VII 98.0 7 1153.0                                                          16 VIII 148.0 6 1253.0                                                        17 IX 288.0 8 1033.0                                                        ______________________________________                                    

Applications

The compounds of the present invention have tremendous spreadabilitywhen applied to substrate. This spreadability results in thin highlylubricating films. The thinness of the film makes the delivery of anexpensive fluoro compound cost effective on many substrates, since theweight of film per area of substrate treated is quite surprisingly low.

Spreadability Test

10 microliters of sample was applied to a polyethylene film and the areacovered by the spreading of the material was evaluated. The valueobtained was compared to water and nonylphenol that has been ethoxylatedwith nine moles of ethylene oxide.

Spreadability

    ______________________________________                                        Sample Tested        Spread Area (Cm.sup.2)                                   ______________________________________                                        Example 15           502.0                                                      Example 17 486.0                                                              Ethoxylated Nonyl phenol (9 moles) 99.3                                       Carboxy Silicone (U.S. Pat. 5,296,625) 127.7                                Example 22                                                                        Water                64.6                                                 ______________________________________                                    

Relative Spreadability

    ______________________________________                                        Sample Tested        Spread Area (Cm.sup.2)                                   ______________________________________                                        Example 15           7.8                                                        Example 17 7.5                                                                Ethoxylated Nonyl phenol (9 moles) 1.5                                        Carboxy Silicone (U.S. Pat. 5,296,625) 2.0                                  Example 22                                                                        Water                1.0                                                  ______________________________________                                    

As can be seen by the above data, the fluoro alkoxylated ester of thecurrent invention is by far the best spreading agent of those tested.NP-9 is a standard fatty surfactant, and the carboxy silicone of theO'Lenick invention is the closest silicone analogue of the currentinvention. All materials clearly spread less well than the products ofthe current invention.

What is claimed:
 1. A fluoro ester conforming to the followingstructure;

    CF.sub.3 (CF.sub.2).sub.x CH.sub.2 CH.sub.2 --O--R--C(O)--R"--C(O)--OH

wherein; R is --(CH₂ CH₂ --O)_(a) --(CH₂ CH(CH₃)O)_(b) --(CH₂ CH₂ O)_(c)--; R" is --CH₂ --CH₂ ; a, b and c are integers independently rangingfrom 0 to 20, with the proviso that a+b+c is greater than 0; x is aninteger ranging from 1 to
 10. 2. A fluoro ester of claim 1 wherein x is1, a is 20, b is 20 and c is
 20. 3. A fluoro ester of claim 1 wherein xis 2, a is 10, b is 5 and c is
 10. 4. A fluoro ester of claim 1 whereinx is 4, a is 0, b is 10 and c is
 0. 5. A fluoro ester of claim 1 whereinx is 6, a is 5, b is 5, and c is
 5. 6. A fluoro ester of claim 1 whereinx is 10, a is 5, b is 1 and c is
 5. 7. A fluoro ester of claim 1 whereinx is 8, a is 10, b is 0 and c is
 0. 8. A fluoro ester of claim 1 whereinx is 10, a is 5, b is 0 and c is 0.